CN103012501A - Zn-Tb coordination polymer luminescent material based on like-amino acid ligand and preparation method thereof - Google Patents
Zn-Tb coordination polymer luminescent material based on like-amino acid ligand and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Zn-Tb coordination polymer yellow-green luminescent material based on a rigid like-amino acid ligand and a preparation method thereof. The chemical formula of the luminescent material is {[Tb(HMIDC)2.2H2O][Zn(HMIDC)2].4H2O}n, wherein n is greater than 1; and the material can be excited by near ultraviolet and emit yellow-green fluorescence. According to the invention, the prepared polymer yellow-green luminescent material crystal containing Zn-Tb mixed metal has relatively good crystallinity, high thermal stability and good luminescence property and is non-toxic and pollution-free, and the cost of the raw materials is low; the preparation technology adopts simple equipment, realizes good comprehensive performance and is suitable for industrial production; and the material can meet the requirements of the application fields of detection, information and illumination of clinical examination, public place display, household appliances and the like. The material has broad application in the aspects of rare earth three-band fluorescent lamp, large-screen and high-definition color TV display, rare earth fluorescent powder, the luminescent material of beacon lights of stations and wharfs and the like.
Description
Technical field
The present invention relates to rare earth luminescent material field, be specifically related to a kind of Zn-Tb hybrid metal ligand polymer yellow-green colour luminescent material based on the category of rigid amino acid ligand and preparation method thereof.
Background technology
In recent years, rare-earth trichromatic luminescent material, especially lamp phosphor, optical memory material, the advantage such as luminous efficiency is high owing to having, the life-span is long, color developing is good, throwing light on and the demonstration field is widely used.Up to now, rare-earth trichromatic luminescent material and preparation method thereof be always adulterate trivalent europium ion yttrium oxide as rouge and powder, using many magnesium aluminates of trivalent terbium ion and trivalent cerium ion codoped as many magnaliums acid barium of green powder, the divalent europium of usining doping as blue powder, while preparing luminescent material, by three kinds of materials high temperature sintering after ground and mixed in proportion, finally obtain practical rare-earth trichromatic fluorescent powder.Although the rare earth luminescent material glow color is abundant, the rare earth green luminescent material kind is relatively less, and it is poor that the aluminates system luminescent material has moisture resistance, has the shortcomings such as glow color is single.And, for the compound based on pure rare earth, to prohibit (Laporte selects rule) because the f transition of electron is subject to parity and cause quantum yield low, fluorescence efficiency is low.Although prepared a plurality of rare-earth doping fluoride nano crystalline substances, there is high photochemical stability, narrow linewidth, long fluorescence lifetime, luminous efficiency advantages of higher, can be used as Multifunction fluorescent mark and nuclear magnetic resonance development reagent, for medical field out-phase or homogeneous analysis, infra-red detection etc.But, doping type device preparation technology complexity, cost is high, and host and guest's build device often there will be phenomenon of phase separation, and device efficiency is reduced, and the wavelength of material almost limits, is very difficultly modified as required.And that hybrid metal coordinates is synthetic, method commonly used is by rare earth compound, as doping agent, is distributed in transition-metal coordination unit or polymkeric substance.But, due to rare earth compounding, in polymeric matrix, exist dispersiveness not good, be easy to and the shortcomings such as matrix phase separates, cause the dopant material poor stability, concentration quenching occurs between fluorescence molecule, fluorescence intensity descends.And pass through rear transition metal (as d
10the electronic configuration metal), by sensibilized, make this polymkeric substance possess the good fluorescence property that more single rare earth or single transition metal ion organic framework materials are not had.The introducing of hybrid ionic also can reduce O – H in the rare earth ion title complex, C – H chemical bond etc., alters the energy delivery pathways of nonradiative transitions such as jumping reducing vibrational relexation, transfer transport, between being, thereby strengthens fluorescence quantum efficiency and extend fluorescence lifetime.Tb
3+the characteristic green emitted of tool, and luminous intensity is high, and quantum yield is high, so around Tb
3+the luminescent material of synthetic different substrates is the interested research topics of people always.Our synthesizing rare-earth-transition metal hybridized polymer, make up the precious metal Os based on single, the more fixing defect of emission wavelength of Ir title complex, the electric charge transition of sensitization rare earth ion, reach the purpose that obtains the yellow-green fluorescence material that fluorescence intensity is large, thermostability is high, the life-span is long.
Summary of the invention
The present invention, in order to overcome above-mentioned the deficiencies in the prior art, provides a kind of colorless single-crystal shape that is, and luminosity is high, can launch Zn-Tb hybrid metal ligand polymer luminescent material based on the category of rigid amino acid ligand of strong yellow-green light and preparation method thereof.
The present invention is the deficiency solved the problems of the technologies described above, and the technical scheme adopted is: the Zn-Tb ligand polymer yellow-green colour luminescent material based on the amino acid part, the chemical formula of described luminescent material is: { [Tb (HMIDC)
2 .2H
2o] [Zn (HMIDC)
2]
.4H
2o] }
n, wherein n is greater than 1, and this material can be by near ultraviolet excitation, and launches strong green fluorescence.
The preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part comprises the following steps:
One, get glyoxal ethyline 4, the 5-dicyan adds in the there-necked flask that fills distilled water, add glacial acetic acid solution after stirring and dissolving and be incubated 3～4 hours, then add NaOH solution, obtain intermediate solution, intermediate solution is added in rare HCl solution and reacted again, after reaction finishes, reaction solution is poured in frozen water, separate out white solid organic ligand H after further cooling
3mIDC, described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and molecular formula is as follows:
Two, get the organic ligand H that step 1 makes
3in the water-soluble mixed solution with organic solvent of MIDC, and add Tb
4o
7and Tb (NO
3)
36H
2a kind of and the Zn (ClO of O
4)
2a kind of with ZnO, use magnetic stirring apparatus to stir at normal temperatures and pressures 10～30min, then adds rare HNO
3regulating the pH value is 3.0～6.0, obtains precursor liquid, standby;
In the mixed solution of above-mentioned water and organic solvent, the volume ratio of water and organic solvent is 0.1:1～2:1, and wherein, organic solvent is ethanol or propyl alcohol.
Three, precursor liquid step 2 made moves in the teflon-lined hydrothermal reaction kettle, add DMF, put into baking oven after sealed reactor, the temperature of regulating baking oven is 140～180 ℃, reaction 60～90h, after question response finishes, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, finally collects the colourless crystallization that the reactor inner bottom part occurs, and the crystallization of collecting is washed 2～3 times with the mixing solutions of ethanol and water, obtain clear crystal shape product luminescent material after drying.
Every 1g glyoxal ethyline 4 in described step 1, the 5-dicyan adds the glacial acetic acid solution that 3～4ml concentration is 0.5～2mol/L.
Every 1g glyoxal ethyline 4 in described step 1, the 5-dicyan adds the NaOH solution that 3～4ml concentration is 0.5～2mol/L.
Every 1g glyoxal ethyline 4 in described step 1, the 5-dicyan is used rare HCl solution that 3～6ml concentration is 0.5～2mol/L.
Every 0.1mol organic ligand H in described step 2
3mIDC adds the mixed solution of 10～40ml water and organic solvent.
Every 0.1mol organic ligand H in described step 2
3mIDC adds the Tb of 0.01～0.02mol
4o
7perhaps Tb (NO
3)
36H
2o.
Every 0.1mol organic ligand H in described step 2
3mIDC adds the Zn (ClO of 0.03～0.08mol
4)
2perhaps ZnO.
Every 0.1mol organic ligand H in described step 3
3mIDC adds the DMF of 1～4ml.
The add-on of above each reactant and solvent is the scope of best add-on, not only the add-on in this scope could realize whole preparation result, and how many of the add-on of each reactant and solvent have influence on degree that reaction carries out and the yield of product.
beneficial effect:
The polymkeric substance yellow-green colour luminescent material crystal structure that contains the Zn-Tb hybrid metal prepared by the present invention is better, nontoxic, pollution-free, and thermostability is high, and luminescent properties is good, and raw materials cost is low; Preparation technology's equipment is simple, convenient operation.In conjunction with the amino-acid compound fluorescent material based on Zn in the past, we use brief and the synthetic Zn-Tb hybrid metal ligand polymer of amino acid part rigidity can make electronics be easy to transmit, and fluorescence efficiency raises, Zn in molecule (MIDC)
2fragment can be served as rare earth luminous antenna, increases luminous intensity.Obtained the yellow-green colour luminescent material of high comprehensive performance, be applicable to suitability for industrialized production, this material can meet electronic industry, and public place shows, the requirement of the demonstrations such as household electrical appliance, information, illumination Application Areas.This material is at the rare-earth trichromatic luminescent lamp, giant-screen and high definition colour TV demonstration aspect, and fluorescent RE powder, the aspects such as luminescent material of station terminal beacon light have wide purposes.
The accompanying drawing explanation
Fig. 1 is the comparison diagram of the PXRD of X-ray diffraction (XRD) collection of illustrative plates of the embodiment of the present invention 1 prepared product and single crystal diffraction digital simulation;
Fig. 2 is the infared spectrum figure of the embodiment of the present invention 1 prepared product;
Fig. 3 is the basic cell structure figure of the embodiment of the present invention 1 prepared product;
Fig. 4 is the fluorescence emission spectrogram of the embodiment of the present invention 1 prepared product.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
The present embodiment is preferred forms of the present invention.
Raw material: glyoxal ethyline 4,5-dicyan, Glacial acetic acid, dilute hydrochloric acid, NaOH solution, ethanol, DMF, Tb
4o
7, be analytical pure, respectively by Shanghai traditional Chinese medicines company, Tianjin great Mao company, Xi'an pharmaceuticals, Luoyang chemical reagents corporation, the supplies of material such as Beijing Feng Tesi chemical materials company limited.
One, prepare organic ligand:
A, measure 50mL distilled water and move in there-necked flask, take the glyoxal ethyline 4 of 5g, the 5-dicyan adds in there-necked flask, and stirs the zeolite that adds 12 g in batches, prevents bumping.
The Glacial acetic acid that adds 15 ml concentration 2mol/L in b, the solution that makes at step a, after adding, insulation is 3.5 hours, add again the approximately NaOH solution of 15 ml concentration 2mol/L, obtain intermediate solution, and then intermediate solution is poured in rare HCl solution of 15ml concentration 2mol/L, after question response liquid is slightly cold, pour in frozen water, separate out the 3g white solid after further cooling, organic ligand glyoxal ethyline 4,5-dicarboxylic acid (H
3mIDC);
Described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and chemical formula is as follows:
Two, prepare precursor liquid:
C, get the organic ligand H that the 0.3mmol step 1 makes
3mIDC is dissolved in the mixed solution of 30ml water and organic solvent, obtains solution C;
In the mixed solution of described water and organic solvent, the volume ratio of water and organic solvent is 0.5:1, and organic solvent is DMF;
D, get the Tb of 0.05mmol
4o
7zn (ClO with 0.1mmol
4)
2add in the solution E of 20ml, after stirring, obtain solution D;
E, the solution D made in steps d is stirred to 20 min at normal temperatures and pressures with magnetic stirring apparatus, then add rare HNO
3, regulating the pH value is 3.0, obtains precursor liquid E, standby.
Three, prepare luminescent material:
F, the precursor liquid E that step e is made are transferred in the teflon-lined hydrothermal reaction kettle, and add the DMF of 12 ml, strengthen organic ligand H
3the dissolving of MIDC, sealed reactor, and reactor is put into to baking oven, and select temperature controlling mode to be reacted, temperature is controlled at 160 ℃, after reacting 72 h, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, and collects the colourless crystallization that the reactor inner bottom part occurs, then adopts the mixing solutions of ethanol and water to wash 2 ~ 3 times the crystallization of collecting, be placed in vacuum drying oven dry under 50 ℃, obtain product and be luminescent material.
Reaction formula is as follows:
By products therefrom { [Tb (HMIDC)
2 .2H
2o] [Zn (HMIDC)
2]
.4H
2o}
nwith German Bruker SMART APEX II type Single Crystal X-ray diffractometer, analyzed, as shown in Figure 1: find to obtain product
The PXRD collection of illustrative plates with for the PXRD collection of illustrative plates of collecting the single crystal diffraction digital simulation, match, at 2 θ, be 7.5,14.2,17.9,22.1, strong characteristic diffraction peak, appear in the places such as 36.1,42.2, obtains the product monocrystalline simultaneously, shows that product is comparatively pure.
The crystalline structure data are as shown in table 1:
Table 1 polymkeric substance { [Tb (HMIDC)
2 .2H
2o] [Zn (HMIDC)
2]
.4H
2o}
ncrystallographic data
By products therefrom { [Tb (HMIDC)
2 .2H
2o] [Zn (HMIDC)
2]
.4H
2o}
nwith U.S. Nicolet 6700 Fourier infrared spectrographs, analyzed, the infrared spectra recorded as shown in Figure 2, at 3010 cm
-1place is weak and wide peak is the vibration of water molecules hydroxyl, at 3000～2800 cm
-1what wave-number range was corresponding is the flexible shock absorbing spectrum of C-H.At 1538 cm
-1, 1470 cm
-1, 1380 cm
-1symmetry and the asymmetric vibration peak of corresponding part carboxyl, its difference is less than 200 cm
-1, show that the carboxyl of part had both adopted the monodentate ligand pattern, also adopt the chelating pattern.The peak of observing toward the long wave place has again proved the existence of imidazole ring.
Draw the molecular structure of the crystal of product by Diamond 3D analogue crystals software, as shown in Figure 3.
At room temperature F4500 fluorescence spectrophotometer for products therefrom (Japan produces) is analyzed, the fluorescence spectrum figure recorded as shown in Figure 4, this product excites under the near-ultraviolet light condition of 285 nm, the emitting fluorescence peak is at visibility region 486 nm, the appearance such as 636 nm, especially the most powerful emmission spectrum appears in yellow green light zone 546 nm.
Products therefrom is carried out to ultimate analysis with gondola Flash EA-2000 elemental analyser, the analysis showed that, material consists of the following composition: compound is C
12h
17n
4o
13tbZn, Theoretical Calculation constituent content per-cent: C 22.19, and H 2. 63, N8.63, practical measurement: C 22.17, H 2.67, and N 8.66.
From thermogravimetric analysis figure, can find out, from room temperature to approximately 200 ° of C materials are lasting weightless, the mass percent lost is approximately 10. 2%, at first corresponding polymer molecule loses 4 free water moleculess, about 400 ° of C organic ligands, start to decompose greatly, slowly weightless, skeleton starts to cave in.To 900 ° of C quality also reducing.
Embodiment 2:
One, prepare organic ligand:
A, measure 50mL distilled water and move in there-necked flask, take the glyoxal ethyline 4 of 10g, the 5-dicyan adds in there-necked flask, and stirs the zeolite that adds 10 g in batches, prevents bumping.
The Glacial acetic acid that adds 30 ml concentration 1mol/L in b, the solution that makes at step a, after adding, insulation is 4 hours, the NaOH solution that adds again 30 ml concentration 1.5mol/L, obtain intermediate solution, and then intermediate solution is poured in rare HCl solution of 40ml concentration 1mol/L, pour in frozen water after question response liquid is slightly cold, separate out 5g white solid organic ligand glyoxal ethyline 4,5-dicarboxylic acid (H after further cooling
3mIDC);
Described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and structural formula is as follows:
Two, prepare precursor liquid:
C, get the organic ligand H that the 0.1mmol step 1 makes
3mIDC is dissolved in the mixed solution of 40ml water and organic solvent, obtains solution C;
In the mixed solution of described water and organic solvent, the volume ratio of water and organic solvent is 0.1:1, and organic solvent is ethanol;
D, get the Tb of 0.01mmol
4o
7zn (ClO with 0.08mmol
4)
2add in the solution E of 20ml, after stirring, obtain solution D;
E, the solution D made in steps d is stirred to 30min at normal temperatures and pressures with magnetic stirring apparatus, then add rare HNO
3, regulating the pH value is 4.0, obtains precursor liquid E, standby.
Three, prepare luminescent material:
F, the precursor liquid E that step e is made are transferred in the teflon-lined hydrothermal reaction kettle, and add the DMF of 3 ml, strengthen organic ligand H
3the dissolving of MIDC, sealed reactor, and reactor is put into to baking oven, and select temperature controlling mode to be reacted, temperature is controlled at 150 ℃, after reacting 72 h, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, and collects the colourless crystallization that the reactor inner bottom part occurs, then adopts the mixing solutions of ethanol and water to wash 2 ~ 3 times the crystallization of collecting, be placed in vacuum drying oven dry under 60 ℃, obtaining product is the white powder luminescent material.
Embodiment 3:
One, prepare organic ligand:
A, measure 50mL distilled water and move in there-necked flask, take the glyoxal ethyline 4 of 5g, the 5-dicyan adds in there-necked flask, and stirs the zeolite that adds 12 g in batches, prevents bumping.
The Glacial acetic acid that adds 15 ml concentration 1.5mol/L in b, the solution that makes at step a, after adding, insulation is 3 hours, the NaOH solution that adds again 15 ml concentration 2mol/L, obtain intermediate solution, and then intermediate solution is poured in rare HCl solution of 30ml concentration 1.5mol/L, pour in frozen water after question response liquid is slightly cold, separate out 3.5g white solid organic ligand glyoxal ethyline 4,5-dicarboxylic acid (H after further cooling
3mIDC);
Described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and chemical formula is as follows:
Two, prepare precursor liquid:
C, get the organic ligand H that the 0.2mmol step 1 makes
3mIDC is dissolved in the mixed solution of 30ml water and organic solvent, obtains solution C;
In the mixed solution of described water and organic solvent, the volume ratio of water and organic solvent is 1:1, and organic solvent is propyl alcohol;
D, get the Tb (NO of 0.06mmol
3)
36H
2zn (the ClO of O and 0.1mmol
4)
2add in the solution E of 30ml, after stirring, obtain solution D;
E, the solution D made in steps d is stirred to 25min at normal temperatures and pressures with magnetic stirring apparatus, then add rare HNO
3, regulating the pH value is 6.0, obtains precursor liquid E, standby.
Three, prepare luminescent material:
F, the precursor liquid E that step e is made are transferred in the teflon-lined hydrothermal reaction kettle, and add the DMF of 2 ml, sealed reactor, and reactor is put into to baking oven, select temperature controlling mode to be reacted, temperature is controlled at 180 ℃, after reaction 60h, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, and the colourless crystallization of collection reactor inner bottom part appearance, then adopt the mixing solutions of ethanol and water to wash 2 ~ 3 times the crystallization of collecting, be placed in vacuum drying oven dry under 50 ℃, obtaining product is the white powder luminescent material.
Embodiment 4:
One, prepare organic ligand:
A, measure 50mL distilled water and move in there-necked flask, take the glyoxal ethyline 4 of 5g, the 5-dicyan adds in there-necked flask, and stirs the zeolite that adds 10 g in batches, prevents bumping.
The Glacial acetic acid that adds 15 ml concentration 0.5mol/L in b, the solution that makes at step a, after adding, insulation is 3.5 hours, the NaOH solution that adds again 20ml concentration 1.5mol/L, obtain intermediate solution, and then intermediate solution is poured in rare HCl solution of 25ml concentration 0.5mol/L, pour in frozen water after question response liquid is slightly cold, separate out 3.5 g white solid organic ligand glyoxal ethylines 4,5-dicarboxylic acid (H after further cooling
3mIDC);
Described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and chemical formula is as follows:
Two, prepare precursor liquid:
C, get the organic ligand H that the 0.3mmol step 1 makes
3mIDC is dissolved in the mixed solution of 30ml water and organic solvent, obtains solution C;
In the mixed solution of described water and organic solvent, the volume ratio of water and organic solvent is 2:1, and organic solvent is ethanol;
D, get the Tb (NO of 0.08mmol
3)
36H
2zn (the ClO of O and 0.11mmol
4)
2add in the solution E of 40ml, after stirring, obtain solution D;
E, the solution D made in steps d is stirred to 30min at normal temperatures and pressures with magnetic stirring apparatus, then add rare HNO
3, regulating the pH value is 5.5, obtains precursor liquid E, standby.
Three, prepare luminescent material:
F, the precursor liquid E that step e is made is transferred in the teflon-lined hydrothermal reaction kettle, and add the DMF of 3ml, sealed reactor, and reactor is put into to baking oven, the select procedure temperature controlling mode is reacted, temperature is controlled at 160 ℃, after reaction 75h, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, and the colourless crystallization of collection reactor inner bottom part appearance, then adopt the mixing solutions of ethanol and water to wash 2 ~ 3 times the crystallization of collecting, be placed in vacuum drying oven dry under 80 ℃, obtaining product is the white powder luminescent material.
Embodiment 5:
One, prepare organic ligand:
A, measure 50 mL distilled water and move in there-necked flasks, take the glyoxal ethyline 4 of 5g, the 5-dicyan adds in there-necked flask, and stirs the zeolite that adds 10 g in batches, prevents bumping.
The Glacial acetic acid that adds 20 ml concentration 1.5mol/L in b, the solution that makes at step a, after adding, insulation is 3.5 hours, the NaOH solution that adds again 20 ml concentration 1.5mol/L, obtain intermediate solution, and then intermediate solution is poured in rare HCl solution of 30ml concentration 2mol/L, pour in frozen water after question response liquid is slightly cold, separate out 3.3g white solid organic ligand glyoxal ethyline 4,5-dicarboxylic acid (H after further cooling
3mIDC);
Described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and chemical formula is as follows:
Two, prepare precursor liquid:
C, get the organic ligand H that the 0.3mmol step 1 makes
3mIDC is dissolved in the mixed solution of 30ml water and organic solvent, obtains solution C;
In the mixed solution of described water and organic solvent, the volume ratio of water and organic solvent is 1.5:1, and organic solvent is propyl alcohol;
D, get the Tb of 0.08mmol
4o
7add in the solution E of 30ml with the ZnO of 0.15mmol, after stirring, obtain solution D;
E, the solution D made in steps d is stirred to 10min at normal temperatures and pressures with magnetic stirring apparatus, then add rare HNO
3, regulating the pH value is 4.5, obtains precursor liquid E, standby.
Three, prepare luminescent material:
F, the precursor liquid E that step e is made are transferred in the teflon-lined hydrothermal reaction kettle, and add the DMF of 6 ml, sealed reactor, and reactor is put into to baking oven, select temperature controlling mode to be reacted, temperature is controlled at 140 ℃, after reaction 75h, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, and the colourless crystallization of collection reactor inner bottom part appearance, then adopt the mixing solutions of ethanol and water to wash 2 ~ 3 times the crystallization of collecting, be placed in vacuum drying oven dry under 70 ℃, obtaining product is the white powder luminescent material.
Claims (9)
1. the Zn-Tb ligand polymer luminescent material based on the amino acid part, it is characterized in that: the chemical formula of described luminescent material is: { [Tb (HMIDC)
2 .2H
2o] [Zn (HMIDC)
2]
.4H
2o] }
n, wherein n is greater than 1, and this material can be by near ultraviolet excitation, and launches yellow-green fluorescence.
2. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 1 comprises the following steps:
One, get glyoxal ethyline 4, the 5-dicyan adds in the there-necked flask that fills distilled water, add glacial acetic acid solution after stirring and dissolving and be incubated 3～4 hours, then add dilute NaOH solution, obtain intermediate solution, intermediate solution is joined in rare HCl solution and reacted again, after reaction finishes, reaction solution is poured in frozen water, separate out white solid organic ligand H after further cooling
3mIDC, described H
3mIDC is 1H-2-methyl-4,5-imidazole-dicarboxylic acid, and molecular formula is as follows:
Two, get the organic ligand H that step 1 makes
3in the water-soluble mixed solution with organic solvent of MIDC, and add Tb
4o
7and Tb (NO
3)
36H
2a kind of and the Zn (ClO of O
4)
2a kind of with ZnO, use magnetic stirring apparatus to stir at normal temperatures and pressures 10～30min, then adds rare HNO
3regulating the pH value is 3.0～6.0, obtains precursor liquid, standby;
In the mixed solution of above-mentioned water and organic solvent, the volume ratio of water and organic solvent is 0.1:1～2:1, and wherein, organic solvent is ethanol or propyl alcohol;
Three, precursor liquid step 2 made moves in the teflon-lined hydrothermal reaction kettle, add DMF, put into baking oven after sealed reactor, the temperature of regulating baking oven is 140～180 ℃, reaction 60～90h, after question response finishes, the control reactor is cooled to room temperature with the rate of cooling of 5 ℃/h, finally collects the colourless crystallization body that the reactor inner bottom part occurs, and the crystal of collecting is washed 2～3 times with the mixing solutions of ethanol and water, obtain the product luminescent material after drying.
3. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, it is characterized in that: every 1g glyoxal ethyline 4 in described step 1, the 5-dicyan adds the glacial acetic acid solution that 3～4 ml concentration are 0.5～2mol/L.
4. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, it is characterized in that: every 1g glyoxal ethyline 4 in described step 1, the 5-dicyan adds the NaOH solution that 3～4ml concentration is 0.5～2mol/L.
5. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, it is characterized in that: the glyoxal ethyline 4 of every 1g in described step 1, the 5-dicyan is used rare HCl solution that 3～6 ml concentration are 0.5～2mol/L.
6. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, is characterized in that: every 0.1mol organic ligand H in described step 2
3mIDC adds the mixed solution of 10～40ml water and organic solvent.
7. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, is characterized in that: every 0.1mol organic ligand H in described step 2
3mIDC adds the Tb of 0.01～0.02mol
4o
7perhaps Tb (NO
3)
36H
2o.
8. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, is characterized in that: every 0.1mol organic ligand H in described step 2
3mIDC adds the Zn (ClO of 0.03～0.08mol
4)
2perhaps ZnO.
9. the preparation method of the Zn-Tb ligand polymer luminescent material based on the amino acid part as claimed in claim 2, is characterized in that: every 0.1mol organic ligand H in described step 3
3mIDC adds the DMF of 1～4ml.
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Cited By (3)
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|---|---|---|---|---|
| CN103275110A (en) * | 2013-06-18 | 2013-09-04 | 洛阳师范学院 | Highly stable Tb coordination polymer green luminous material and preparation method thereof |
| CN105018073A (en) * | 2015-07-14 | 2015-11-04 | 洛阳师范学院 | Eu complex red luminous crystal material containing two ligands and preparation method of Eu complex red luminous crystal material |
| CN105693779A (en) * | 2016-03-15 | 2016-06-22 | 洛阳师范学院 | Polymer green luminescence material containing Zn-Tb mixed metal and preparation method of polymer green luminescence material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275110A (en) * | 2013-06-18 | 2013-09-04 | 洛阳师范学院 | Highly stable Tb coordination polymer green luminous material and preparation method thereof |
| CN103275110B (en) * | 2013-06-18 | 2015-06-03 | 洛阳师范学院 | Highly stable Tb coordination polymer green luminous material and preparation method thereof |
| CN105018073A (en) * | 2015-07-14 | 2015-11-04 | 洛阳师范学院 | Eu complex red luminous crystal material containing two ligands and preparation method of Eu complex red luminous crystal material |
| CN105693779A (en) * | 2016-03-15 | 2016-06-22 | 洛阳师范学院 | Polymer green luminescence material containing Zn-Tb mixed metal and preparation method of polymer green luminescence material |
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| CN103012501B (en) | 2015-03-11 |
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